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Recycling of vat and reactive dyed textile waste to

new colored man-made cellulose fibers†
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Cite this: Green Chem., 2019, 21,

5598
Simone Haslinger, a Yingfeng Wang,a Marja Rissanen,a Miriam Beatrice Lossa,b
Marjaana Tanttu,c Elina Ilen,c Marjo Määttänen,d Ali Harlin,d Michael Hummel a
and Herbert Sixta *a

The successful recycling of colored textile waste and reuse of respective dyes would represent a major
milestone of global efforts to reduce the environmental impact of the textile industry. The chemical up-
cycling of dyed pre- and postconsumer cotton waste is promoted by studying the spinability and color
fastness of seven vat and reactive dyes (i.e. Indanthren Blue BC 3%, Indanthren Red FBB coll, Indanthren
Brilliant Green FBB coll, Levafix Brilliant Red E-4BA, Levafix Blue E-GRN gran, Remazol Brilliant Blue R
spec, and Remazol Black B 133%) during dry-jet wet spinning. Apart from the fabrics dyed with Levafix
Brilliant Red E-4BA, all samples dissolved in 1,5-diazabicyclo[4.3.0]non-5-ene actetate, a superbase based
ionic liquid, and could be converted to new colored man-made cellulose fibers. It was found that there is
a clear discrepancy between the recyclability of dyed pre- and postconsumer cotton waste, resulting in
significantly higher fiber properties up to tenacities of 59.8 cN/tex and elongations of 13.1% in case of the
latter. All recycled fibers displayed a noticeable color change in the CIELab space (ΔE = 8.8–25.6)
throughout the spinning process. Despite these deviations, almost all fibers and demo fabrics produced
Received 6th August 2019, thereof exhibited bright colors that can be reused in textile industry. Only Remazol Black B 133% did not
Accepted 18th September 2019
sufficiently translate to the new textile product. The wash and rubbing fastness of the fabrics knitted from
DOI: 10.1039/c9gc02776a the regenerated fibers was superior to the dyed waste fabrics mainly because of the homogenous distri-
rsc.li/greenchem bution of the dyes along the fiber cross-section.

Introduction Various strategies for the conversion of cotton waste gar-

ments into new value added products have been developed
Fast fashion has transformed the perception of clothing from over the past decades. They can mainly be divided into chemi-
a valuable, long-lasting product into a short-term use, disposa- cal and mechanical approaches. In the latter, cotton waste is
ble good.1 Europe only recycles 25% of its textile waste, the shredded, opened, and carded to reclaim single cotton fibers.4
vast majority is incinerated or landfilled. Cotton is considered Dependent on their final application, these can be pretreated
a renewable resource, but its ecological footprint is equal or or bleached before they are respun into new yarns.5 However,
even larger than the impact of polyester.2 When cotton is strategies to preserve and reuse the original color are urgently
however recycled, its carbon footprint can be cut into half as needed to avoid the generation of further effluents such as
further cotton cultivation is minimized.3 wastewater from dyeing.6 Textile dyeing can require up to 150
liters of water per kilogram of fabric. In developing countries,
where most of the production takes place and where adequate
a
Department of Bioproducts and Biosystems, Aalto University, P. O. Box 16300, environmental legislation is often lacking, the wastewater is
Espoo, FI-00076 Aalto, Finland. E-mail: [email protected], frequently discharged unfiltered into waterways. 700 000 tons
[email protected], [email protected], [email protected], of synthetic dyes are produced worldwide. Up to 200 000 tons
[email protected]
b of these dyes are lost to effluents every year during dyeing and
Department of Chemistry and Biology, Hochschule Fresenius, University of Applied
Science, Limburger Str. 2, 65510 Idstein, Germany. finishing operations of textiles, due to the inefficiency of the
E-mail: [email protected] dyeing processes.7
c
Department of Design, Aalto University, Otaniementie 13, 02150 Espoo, Finland. In the recent past, some mechanical recycling technologies
E-mail: [email protected], [email protected] have emerged, aiming at color retention during the reuse of
d
VTT Technical Research Centre of Finland Ltd, P.O. Box 1000, Espoo, FI-02044 VTT,
textile waste. The mechanical recovery of cotton circumvents
Finland. E-mail: [email protected], [email protected]
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ both, cotton cultivation and dyeing, by sorting the raw-
c9gc02776a material prior to the yarn manufacturing. The waste material

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is subjected to a process similar to ginning to clean and open accumulation in the coagulation bath, which would affect the
the cotton fibers.8 By blending different colors, a broad spec- solvent recycling procedure and compromise the overall
trum of yarns can be obtained, which show properties similar economy of the process. This recycling route, in which the dye
to conventional yarns produced from virgin materials.9 The is co-dissolved with the polymer, can be compared to spin
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drawback is that the raw-material consists of mainly pre-consu- dyeing, which is frequently used for synthetic polymers. Spun-
mer cotton waste, whereas only small amounts of postconsu- dyed fibers have a considerably reduced environmental impact
mer cotton can be added to the yarn production.4,9 Nowadays, compared to classical textile dyeing.26 Initial studies have
75% of pre-consumer cotton is reused,3 while postconsumer reported the spin dyeing of Lyocell fibers through the addition
waste is more problematic to recycle due to coloring, impuri- of inorganic pigments,27 different colorants and their precur-
ties and degradation induced by sun light irradiation, mechan- sors28 to the spinning solution. Also vat-dyed pulp mixed with
Open Access Article. Published on 18 September 2019. Downloaded on 2/12/2025 5:14:56 AM.

ical abrasion, and laundering.10,11 undyed pulp was found to result in a good colorfastness.29,30
Therefore, chemical recycling offers more options for post- Vat dyes are water insoluble in their oxidized form, but dis-
consumer waste. Recent studies have shown that cotton from solve in water once reduced. This enables them to be precipi-
textiles can be used to produce biogas,12 cellulose nano- tated on the fiber surface by a sequence of reduction and oxi-
particles,13 aerogels14 or microcrystalline cellulose.15 When it dation reactions. Moreover, vat dyes, such as Indanthrenes, are
comes to textile industry, a cradle-to-cradle approach is more thermally stable due the presence of anthraquinone units. In
desirable, implying that textile waste is dissolved and re-spun the 1960s, 40–50% of all cellulosics were dyed with vat dyes
into new fibers. In 2016, we demonstrated the conversion of because of their excellent resistance to acid, alkali, and bleach-
white post-consumer cotton to Lyocell type fibers by dry-jet wet ing. Nowadays, vat dyeing is still used for textile products that
spinning using the ionic liquid 1,5-diazabicyclo[4.3.0]non-5- require to withstand a large number of washing cycles or
ene actetate [DBNH] [OAc] as a direct solvent. The procedure industrial laundering, including work wear, household
first requires assessing the viscoelastic properties of the result- articles, and outdoor equipment. With the development of
ing solution, which are entirely determined by the cotton more stable and cost-effective reactive dyes, vat dyes lost their
waste material. Dependent on how heavily the fabric was used dominant position on the market. Today, the global share of
and washed, its properties might be suitable for dry-jet wet reactive dyes amounts 20–30%, which involves the dyeing of
spinning without any further pretreatment.16 In many cases, most cellulose products. Reactive dyes consist of four units,
the degree of polymerization of cellulose, however, needs to be most commonly referred to as solubilizing, chromophore,
lowered by hydrolysis to a target value to fit the requirements bridging, and reactive groups.31 Comparable to vat-dyes, reac-
of the spinning process.16,17 Besides the adjustment of macro- tive dyes with anthraquinone chromophores are considered to
molecular properties, the pretreatment can also involve purifi- be more resistant to laundering, elevated temperatures, and
cation steps such as bleaching and the removal of metals.18 A bleaching than azo colorants.32,33 The reactive groups of reac-
bleached product has so far been more preferable on a com- tive dyes can mainly be divided into halo heterocycles that
mercial scale due to hygiene and aesthetic reasons, although it form a covalent bond with cellulose via nucleophilic substi-
increases the consumption of chemicals and water, also tution, and activated vinyl compounds such as vinyl sulfones
demanding subsequent re-dyeing. It is evident that these that attach to cellulose through addition reactions.31 Finally,
approaches do not sufficiently comply with the principles of the reactivity of these units and the nature of the chromophore
green processing. A recycling strategy is hence only truly sus- determine the color fastness of a garment throughout its life-
tainable if the original color of a waste fabric can be translated cycle as well as its subsequent recyclability.
to the new product directly. As mentioned before, no studies have yet systematically
Preliminary studies have shown that it is, in principle, poss- investigated the role of different dye classes in a chemical
ible to dissolve dyed textile waste and to spin new colored upcycling process for cotton based textile waste, which none-
fibers thereof. This can be achieved via different systems such theless appears essential to prevent an extensive consumption
as the viscose process,19 the NMMO-based Lyocell process,20 of chemicals and water. For the first time, this study targets to
alkali/urea,21 or a mixture of 1-butyl-3-methylimidazolium create a better understanding of the recyclability of dyed
acetate and DMSO.22 Similarly, [DBNH] [OAc] can be used to cotton fabrics within a dry-jet wet spinning process, using a
recycle colored textile waste.23 However, there are more than superbase based ionic liquid such as [DBNH] [OAc] (Ioncell™),
10 000 different dyes used in textile manufacturing and identi- by assessing the impact of seven commercial colorants onto
fying the exact chemical compound(s) in textile waste is nearly the production of man-made cellulose fibers. We tested three
impossible.24 Therefore, more systematic studies are needed to vat dyes (Indanthren Blue BC 3%, Indanthren Red FBB coll,
discern categories of textile dyes that are suitable for chemical Indanthren Brilliant Green FBB coll) and four reactive dyes,
textile recycling. Respective dyes have to maintain their mole- among them two vinyl sulfone dyes (Remazol Brilliant Blue R
cular integrity when exposed to the chemical environment and spec, Remazol Black B 133%), and two halo quinoxaline dyes
thermal impact of the fiber spinning process. Further, they (Levafix Brilliant Red E-4BA, Levafix Blue E-GRN gran). Pre-
should not alter the rheological properties of the spin dope, and post-consumer cotton waste was used as textile substrate.
which could impair its subsequent spinability.25 Finally, the The white fabrics were dyed, ground, and their intrinsic
dyes have to coagulate with the cellulose to avoid their viscosities were measured. This approach was chosen because

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the exact dye formulation of waste textiles is usually unknown.

In this way, it was possible to relate the process behavior and
color stability to the particular dye during the entire spinning
process.
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The pre-consumer fabric was pretreated with electron beam

irradiation, sulfuric acid and endoglucanases to adjust the
degree of polymerization. The effect of the pretreatment was
assessed based on the molar mass distributions, and com-
pared to the properties of untreated dyed post-consumer
waste. Subsequently, the samples were subjected to dry-jet wet
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spinning and if spinable processed to knitted fabrics. Besides

the determination of tensile properties and fiber orientation,
the color change of the dyes throughout the spinning process
was monitored, together with their subsequent fastness to
washing and rubbing. Ultimately, final prototype garments
were manufactured from staple fibers spun directly from solu-
tions of worn dyed textile fabrics to demonstrate that the
dyeing of white textile waste corresponds to that of genuine
dyed textile waste in terms of recyclability.

Materials and methods

Raw material
White pre-consumer cotton (100%) was purchased from
Iisalmen Kangastukku (Finland). The product name was
Painopohja ( printing base) and consisted of a plain weave
structure (148 g m−2). White postconsumer hospital bed
Fig. 1 Chemical structure of the vat and reactive dyes used.
sheets (100% cotton) were supplied by the Uusimaa Hospital
Laundry (Uudenmaan Sairaalapesulo Oy, Finland). As all
samples displayed distinct viscoelastic properties, the limiting
viscosity of each bed sheet was determined separately accord- ing of color could be observed anymore. Reactive dyeing was
ing to the SCAN-CM 15:88 standard of cellulose in cupri-ethyle- conducted in a washing machine (Esteri Pesukoneet Oy,
nediamine (CED) solution. Moreover, all samples were ground Vantaa, Finland) using a 60 °C/20 l program with the following
using a Wiley Mill and their dry-matter content was dyeing sequence: Prewetting + gentle spin–dyeing–rinsing–
determined. boiling–rinsing–spin. As in the previous procedure, the reac-
tive dyes amounted 2% of the dry mass of the cotton samples.
Dyes and dyeing procedures The sample to liquor ratio was 1 : 20 (kg l−1). Na2SO4·10H2O
Indanthrene Red FBB coll (C.I. Vat Red 10), Indanthren (50 g l−1) was added to increase the affinity of the dyes to
Brilliant Green FBB coll (C.I. Vat Green 1), Levafix Brilliant Red cotton, while Na2CO3 (9 g l−1) was used to provide an alkaline
E-4BA (C.I. Reactive Red 158), and Levafix Blue E-GRN gran environment. After dyeing, all fabrics were air-dried.
(C.I. Reactive Blue XX) were kindly provided by DyStar
(Germany). Indanthren Blue BC 3% (C.I. Vat Blue 6), Remazol Pretreatment of pre-consumer cotton
Brilliant Blue R spec (C.I. Reactive Blue 19) and Remazol Black Waste cotton was pretreated in three different ways using acid
B gran 133% (C.I. Reactive Black 5) were purchased from A. hydrolysis (A), electron beam irradiation (e-beam), and
Wennström Oy (Finland). The chemical structures of the dyes sequences of enzymatic treatment with endoglucanases (EG)
can be found in Fig. 1. and acids (A) to reduce the degree of polymerization (DPv) to
All fabrics were dyed in 1 kg batches. During vat-dyeing, an intrinsic viscosity of 450 ± 50 ml g−1 (DPv = 1050 ± 100).
water (20 l) was heated in a kettle (50 °C) and Na2S2O4 (3 g ml−1), (A): Sulfuric acid (H2SO4, 95–97%, Merck or Sigma) was
25 wt% sodium hydroxide (NaOH) and Na2SO4·10H2O diluted to 0.27 M and heated to 82 °C. Subsequently, ground
(12 g l−1) were added. Once the respective Indanthrene dye cotton was added in a sample to liquor ratio of 3 : 100 and
(2% of the dry weight of the samples) had been dissolved and treated 7–9 min to yield a target viscosity of 450 ± 50 ml g−1.
reduced, the cotton fabrics were soaked in the dyeing bath for After the treatment, the sample was washed with cold de-
45 min under constant stirring. In order to enhance the oxi- ionized water to stop the reaction.
dation of the dyes, the fabrics were subsequently rinsed with (E-beam): The electron beam pretreatment was conducted
water followed by hydrogen peroxide (2 ml l−1) until no leach- by means of a 10 MeV accelerator at Leoni Studer AG

5600 | Green Chem., 2019, 21, 5598–5610 This journal is © The Royal Society of Chemistry 2019
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(Switzerland). A series of different electron beam dosages Gebr. Kufferath AG, Germany). The resulting dope was then
(5–30 kGy) were tested to reach the required viscosity. shaped into a cylindrical mold and stored upon solidification
(EG-A, A-EG): The sequences of endoglucanase and acid (1–7 days, 5–8 °C). The viscoelastic properties of the spinning
treatments were carried out by VTT (Finland). The shredded solution were evaluated on an Anton Paar Physica MCR 300
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vat-dyed cotton material was treated with an endoglucanase- rheometer and on an Anton Paar Physica MCR 302 rheometer
rich enzyme Ecopulp R (AB Enzymes, Finland) at a consistency (Austria). A dynamic frequency sweep test (100–0.1 s−1) was
of 25 wt% for 4 h at 50 °C. Prior the treatment, the cotton used to obtain the complex viscosity η* and the dynamic
sample was dispersed in water to 2 wt% and subsequently moduli (G′, G″) as a function of the angular frequency ω.
dewatered to enhance the enzymatic treatment. The enzyme Assuming the validity of the Cox-Merz rule, an apparent zero
dosage was 10 mg protein per g of cotton pulp. After the reac- shear viscosity η0* of the spinning solutions could be calcu-
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tion had been stopped (90 °C, 30 min), the fibrillated material lated, and the crossover point of G′ and G″ was determined to
was cooled and rinsed with deionized water. The acid treat- yield additional information on the cellulose substrate.36
ment was carried out for 2 h at 90 °C at a consistency of
10 wt% (oven dry cotton/water). The pre-heated cotton material Dry-jet wet spinning
was dispersed in water and 0.45 wt% (based on the oven dry The cellulose solution was spun into filaments on a custo-
weight of cotton) of H2SO4 (0.5 M, FF-Chemicals Ab) were mized lab-scale piston unit (Fourne Polymertechnik,
added. Germany). The spin dope was heated according to its rheologi-
After the reaction had been stopped by diluting the mixture cal properties and extruded through a 200-holes spinneret
with deionized water to 5 wt% consistency, the sample was (0.1 mm diameter, 0.02 mm capillary length). While passing a
dewatered and washed with cold deionized water. ca. 1 cm air gap, the filaments were stretched with a draw ratio
of 12 (DR = vtake-up/vextr.). After spinning, the fibers were cut
Molar mass distribution (MMD)
into staple fibers (4 cm), opened, washed with water (80 °C,
The molar mass distribution (MMD) of both dyed pre- and post- 2 h), and air dried.
consumer samples was analyzed by gel permeation chromato-
graphy applying one precolumn (PLgel Mixed-A, 7.5 × 50 mm) Tensile properties and birefringence
and four analytical columns (PLgel Mixed-a, 7.5 × 300 mm). The
The properties of all fibers spun from colored post-consumer
set-up was equipped with a refractive index detector (Shodex
cotton waste including tenacity (cN/tex), elongation at break
RI-101). The samples were dissolved in 90 g l−1 LiCl/N,N-di-
(%), and linear density (dtex) were determined on a Favigraph
methylacetamide (DMAc) via a solvent exchange procedure
device (Textechno, Germany). Test parameters: 20 cN load cell,
(H2O/acetone/DMAc). The system was operated at a temperature
10 mm gauge length, 10 mm min−1 test speed, 100 mg preten-
of 25 °C and a flow rate of 0.75 ml min−1 using 9 g l−1 LiCl/
sion, fiber count 20. All samples were measured in conditioned
DMAc as an eluent. The injection volume was 100 µl. Pullulan
(20 °C, 65% relative humidity) and wet state (10 s wetting prior
standards (Mw 343–708 000 Da) were used as calibration stan-
to the testing). The Young’s Modulus was calculated from the
dards employing a direct-standard calibration model.34
initial slope of the individual stress strain curves. The fibers
[DBNH] [OAc] produced from pretreated, dyed pre-consumer cotton were ana-
lyzed on Vibroskop and Vibrodyn 400 devices (Lenzing,
1,5-Diazabicyclo [4.3.0] non-5-ene (99%, Fluorochem, UK) was
Instrument, Austria). Test parameters: 20 mm gauge length,
neutralized with glacial acetic acid (100%, Merck, Germany).35
20 mm min−1 test speed, 100 mg pretension, fiber count: 10.
Dissolution studies The total orientation of the all fibers was estimated using a
polarizing light microscope (Zeiss Axio Scope, Zeiss AG,
In order to analyze the solubility of the dyes in the ionic
Germany). Fibers showing an average linear density were taped
liquid, small amounts of dye were suspended in [DBNH] [OAc]
to a glass slide, and the birefringence angle was measured for
and stirred under constant heating (80°, 1 h). A drop of the
the bottom, middle, and top part of the fibers. Assuming a
resulting mixture was then placed onto a glass slide and
density of 1.5 g cm−3, the total orientation factor ft could be
observed under a heating microscope (80 °C, Zeiss Axio scope
calculated by dividing Δn by the maximum birefringence value
A1, Zeiss AG, Germany). The same procedure was also con-
of cellulose (0.062).37
ducted for the spinning dopes prepared from the dyed waste
cotton fabrics to evaluate the effect of dyes on the dissolution
Color coordinates and color difference
of the respective cotton substrate.
The optical properties of all samples before and after spinning
Dope preparation and rheology were assessed by CIELab coordinates using a 10 °C observer
After grinding, the dyed fabrics were dissolved in [DBNH] and a standard illuminant D65 (SpectroScan, GretagMacbeth,
[OAc] (80 °C, 90 min) to obtain a 13% cellulose solution using Germany). The difference in color ΔE was calculated from the
a vertical kneader system. After dissolution, undissolved par- following equation,
ticles were removed from the solution by press filtration qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
(80 °C, 1–2 MPa, metal filter fleece, 5–6 µm absolute fineness, ΔE ¼ ðΔL*Þ2 þ ðΔa*Þ2 þ ðΔb*Þ2

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where ΔE denotes the total difference between two colors in Wash fastness
the CIELab space, ΔL* the difference in lightness, Δa* the The color fastness of the dyed fabrics and the fibers after spin-
difference in the red-green axis, and Δb* the difference in the ning was tested according to EN ISO 105-C06 (color fastness to
yellow-blue axis. domestic and commercial laundering). The specimens were
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Yarn spinning and tensile testing sewn together with a DW-multifiber adjacent fabric. If the
specimen was loose fibers, the mass of loose fiber was equal to
The staple fibers were soaked into a spin finishing solution one-half of the combined mass of the adjacent fabrics (multifi-
(50 °C, 5 min) consisting of Aflian CVS and Leomin PN ber and non-dyeable fabrics). The size of cotton fabric speci-
(Archroma, Switzerland). The ratio of Aflian CVS and Leomin men was 100 mm × 40 mm. The mass of regenerated cellulosic
PN was 4 : 1, in total amounting 0.25% of the dry mass of the
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fabric specimens was similar to cotton fabric specimens. The

fibers. The sample to liquor ratio was 1 : 20. After drying, the wash liquor was prepared by dissolving 4 g l−1 of detergent
fibers were opened by a fiber opener (Trash analyzer281C, (AATCC 1993 Standard Reference Detergent WOB) in deionized
Mesdan, Italy). The opened fibers were carded (Carding water. The test method was A1S, where the temperature was
Machine 337A, Mesdan, Italy for the fibers spun from post- 40 °C and the liquor volume was 150 ml. The number of steel
consumer waste or Automatex, Italy for the fibers spun from balls was 10 and the washing time was 30 min. The specimens
pre-consumer cotton). The carded web was formed to a sliver, were washed in the Linitest equipment (Original Hanau,
drafted (Stiro Roving Lab 3371, Mesdan, Italy) and doubled Germany). At the end, the specimens were rinsed twice for
twice, and formed into a roving. The yarn was spun with a 1 min in two separate 100 ml portions of water at 40 °C. The
ring-spinning machine (Ring Lab 82BA, SER.MA.TES, Italy, for specimens were air-dried. The change in color of the specimen
the fibers spun from post-consumer waste, or Ring Lab, and the staining of the multifiber fabric were assessed using
Mesdan, Italy, for the fibers spun from pre-consumer cotton). the grey scales under D65 illumination. The highest value of
The yarn twist direction was Z and twist per meter 700. Both the grey scale is 5 (no color change or staining) and 1 is the
tenacity (cN/tex) and elongation at break (%) of the spun yarns worst (cf. Fig. S1 and S2 in the ESI†).
(single thread) were measured on a MTS 400 tensile tester
(MTS, USA) with a 50 N load cell, a gauge length of 250 mm, Rubbing test
and a test speed of 250 mm min−1. Before the measurement, The color fastness to rubbing of the dyed fabrics and the
the yarns were conditioned (20 ± 2 °C, 65 ± 2% relative humid- regenerated cellulosic knitted fabrics was tested according to
ity) and their average linear density (tex = g per 1000 m) was the EN ISO 105-X12:2016 standard. The specimens were
determined from 20 m skeins. The plied yarn was produced by rubbed 20 times (10 times to and 10 times fro) with a dry
twisting two threads together (DirectTwist®, Agteks, Turkey). rubbing cloth (desized, bleached cotton cloth) and with a wet
The ply twist direction was S with 300 twists per meter. (100% pick-up of water) rubbing cloth. The diameter of the
Demonstration products rubbing finger was 16 mm with a downward force of 9 N. The
test cloth was removed from the finger and air-dried. The
The yarn produced from recycled, Indanthren Blue BC 3% staining of the test cloth was assessed with the grey scale
dyed pre-consumer cotton was employed to produce the baby under D65 illumination.
jacket demonstrator. The base fabric of the baby jacket was
interlock-knit (127 g m−2) using a single thread yarn (18 tex Z Recycling of fibers from worn denim fabrics to a scarf
700), and the sleeve cuffs were 2 × 1 rib-knit using two com- In comparison to the recycling of self-dyed pre-consumer
bined threads together (18 tex Z 700 × t0). The fabrics were cotton waste, a used denim fabric was dissolved directly in
knitted by a flatbed weft knitting machine (Stoll CMS ADF [DBNH] [OAc] and spun into new staple fibers, which were
32W E7.3 multi gauge, Stoll, Germany). Both materials were then processed into a scarf for demonstration purposes. The
finished solely by steam ironing before sewing. The binding individual process steps are described in the ESI (Fig. S7 and
material in the edges was a commercial knitted viscose, Tables S4–S6†).
narrow fabric band. The cotton based sewing yarns are typical
in knit garment production. The garments were sewed in a
prototyping laboratory using industrial-like sewing machinery. Results and discussion
No finishing treatments were applied after sewing.
The blue, plied yarn (221 tex Z 700 × 2 S 300) produced from Raw-material and pretreatment
recycled Remzol Brilliant Blue R spec dyed post-consumer Discarded textiles can be classified as pre- and post-consumer
cotton was used for the scarf demonstrator. The knit structure waste. The former is produced during the manufacturing of
was mixed purl and lace and the same flatbed knitting machine textiles and represents, for example, excess material resulting
was employed as in the baby jacket demonstrator. from cutting clothing patterns. As its properties are usually
For color fastness testing, single jersey fabrics (150 g m−2) well known, pre-consumer cotton shows a significantly higher
were knitted (Stoll CMS ADF 32W E7.3 multi gauge, Stoll, recyclability than post-consumer garments that have under-
Germany) from plied yarns spun from pre- and post-consumer gone a whole lifecycle. When establishing a recycling strategy
cotton. for cotton rich textiles, it is essential to know the origin of the

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product. The molecular properties of pre-consumer cotton to a polydispersity index (PDI) close to 2.0,39 enzymes such as
resemble virgin one with a high intrinsic viscosity of up to endoglucanase result in a broadening of the molar mass distri-
2000 ml g−1. At the same time, these fibers might contain a bution and enhance the cellulose’s reactivity towards the dis-
higher amount of dyes and finishing chemicals. Wearing and solving agent.40 In general, a broad molar mass distribution of
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laundering subsequently decrease the chemicals present in the cellulose substrate can be beneficial for the spinning
the textile product, but also affect the macromolecular mole- process because it contains both long chains for fiber strength
cular properties of cellulose such as the degree of and shorter ones to act as fillers.41 Therefore, enzymatic treat-
polymerization.10,11 This implies that the cotton’s viscosity ments are expected to result in a better spinnability than acid
decreases dependent on the usage, eventually creating a very treatments only. A combination of both is done for cost
heterogeneous post-consumer product. efficiency and to remove possible contaminations by metals.
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In order to study the recyclability of dyed textile waste sys- Adjusting the viscosity by e-beam irradiation appears more
tematically and to gain a better understanding of the associ- sustainable in terms of wastewater generation and saves costs
ated challenges, both pre-consumer and post-consumer cotton emerging from drying after wet-treatment. During e-beam
were used as raw material. The fabrics where then dyed as irradiation, high-energy electrons (10 MeV) penetrate a stack of
described in the Materials and methods section to obtain sub- sheets of cellulose materials (fabric) with almost constant
strates that resemble real waste textiles, but with exact knowl- energy. The resulting radicals are statistically distributed in
edge on the type and amount of dye in the fabric. the material, which leads to a uniform degradation of the cell-
As reported previously, cotton waste needs to show a limit- ulose chains. Due to unsaturated, stable radicals and the for-
ing viscosity of 400–500 ml g−1 to be spun to Lyocell-type mation of labile groups such as carbonyl groups, depolymeri-
fibers using NMMO monohydrate or [DBNH] [OAc] as zation reactions may continue even after the e-beam treatment,
solvent.16 Therefore, the pre-consumer fabric was subjected to especially under alkaline and/or oxidative conditions.42
different pretreatments, such as electron beam irradiation A summary of the studied treatments and their influence
(e-beam), H2SO4 hydrolysis (A), and combinations of acid on the limiting viscosity and molar mass distribution is dis-
washing with H2SO4 (A) and enzymatic hydrolysis with endo- played in Fig. 2a and Table 1.
glucanase (EG), after vat-dyeing with Indanthren Blue BC 3%. The initial viscosity of the Indanthren dyed pre-consumer
The idea of the pretreatments was to adjust the degree of fabric ranged around 2032 ml g−1 and was decreased by
polymerization (DP) of cellulose to a target DP to obtain the e-beam irradiation, acid treatment (A), as well as by EG-A and
viscoelastic properties necessary for optimal spinning while A-EG sequences to 545, 454, 496, and 470 ml g−1, respectively.
maintaining the original color of the fabric. Mechanical treat- Both e-beam and A only had a minor effect on the polydisper-
ments such as disk refining or chemicals that would cause sity index (PDI) of the samples (2.7 and 2.8). Despite the
bleaching (i.e. O3 or H2O2) were thus avoided. similar PDI, it is evident that A tends to degrade rather longer
Sequences of acid washing and endoglucanase treat- polymer chains than shorter ones, which is consequently
ments have yet successfully been employed on other waste reflected in the lower amount of DP > 2000 chains (29.4%)
materials.38 Whereas acids most commonly degrade cellulose compared to the statistical cleavage induced by e-beam

Fig. 2 Molar mass distribution of (a) pre-consumer cotton dyed with Indanthren Blue BC 3% before and after electron beam (e-beam), endogluca-
nase (EG and acid washing (A), acid washing (A) and endoglucanase (EG) pretreatment, and acid washing only (A) as well as (b) the molar mass distri-
bution of post-consumer cotton before and after dyeing with Indanthren, Remazol and Levafix colorants.

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Table 1 Summary of pre- and post-consumer samples studied including their pretreatments, intrinisic viscosities (ml g−1), number average molar
mass Mn (kDA), weight average molar mass (kDA), and poly dispersity index (PDI), as well as high and low molecular weight fractions of cellulose
(DP < 100, DP > 2000, %)
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Viscosity/
Sample Pretreatment (ml g−1) Mn/kDa Mw/kDa PDI DP < 100/% DP > 2000/%

Pre-consumer
Untreated — 2032 ± 50 423.1 ± 1.0 1417.3 ± 57.7 2.4 ± 1.4 0 78.1 ± 0.8
Indanthren Blue BC 3% e-beam 545 ± 11 147.3 ± 3.2 391.1 ± 10.6 2.7 ± 0.1 0.3 ± 0.1 37.8 ± 0.4
Indanthren Blue BC 3% EG-A 496 ± 15 67.1 ± 7.6 304.5 ± 13.4 4.6 ± 0.7 3.6 ± 1.3 24.8 ± 0.5
Indanthren Blue BC 3% A-EG 470 ± 12 75.9 ± 1.2 380.0 ± 55.9 5.0 ± 0.8 2.7 ± 0.2 28.1 ± 0.5
Open Access Article. Published on 18 September 2019. Downloaded on 2/12/2025 5:14:56 AM.

Indanthren Blue BC 3% A 454 ± 11 114.5 ± 14.5 314.9 ± 6.1 2.8 ± 0.4 0.9 ± 0.9 29.4 ± 0.7
Post-consumer
Undyed — 396 ± 16 94.1 ± 4.2 193.8 ± 2.6 2.1 ± 0.1 1.5 ± 0.4 15.3 ± 0.2
Indanthren Brilliant Red FBB — 461 ± 78 93.7 ± 1.5 206.5 ± 3.5 2.2 ± 0.02 1.4 ± 0.06 17.7 ± 0.3
Indanthren Brilliant Green FBB Coll — 435 ± 33 100.1 ± 4.0 210.5 ± 1.0 2.1 ± 0.1 1.3 ± 0.3 18.5 ± 0.02
Remazol Black B gran 133% — 448 ± 113 91.8 ± 0.1 255.3 ± 0.1 2.8 ± 0.003 1.9 ± 0.08 23.1 ± 0.2
Remazol Brilliant Blue R spec — 422 ± 63 91.9 ± 2.5 204.0 ± 0.5 2.2 ± 0.1 1.8 ± 0.2 17.5 ± 0.04
Levafix Brilliant Red E-4BA — 465 ± 28 102.4 ± 5.3 308.3 ± 1.5 3.0 ± 0.1 1.6 ± 0.4 29.1 ± 0.2
Levafix Blue E-GRN gran — 426 ± 56 89.1 ± 1.8 186.8 ± 0.3 2.1 ± 0.04 1.7 ± 0.3 14.3 ± 0.01

irradiation (37.8%). In contrast, both EG-A and A-EG As stated in the Experimental section, bed sheets of varying
sequences substantially increased the PDI of the cotton sub- viscosities were then combined to 1 kg batches, and sub-
strate from 2.4 to 4.6 and 5.0 also leading to a rise in the low sequently dyed with a selection of Indanthren, Remazol, and
molecular weight fractions (DP < 100) with 3.6% and 2.7%, Levafix dyes. Their average molar mass distributions and visc-
respectively. osities can be found in Fig. 2b and Table 1. The viscosities of
The aim for the post-consumer waste was to be used the samples varied from 396 ml g−1 (undyed) to 465 ml g−1
without any pretreatment to exclude possible effects thereof on (Levafix Brilliant Red E-4BA).
the dye structures. All post-consumer samples consisted of The PDI of the bed sheets dyed with Remazol Black B gran
white hospital bed sheets supplied by a laundering company. 133% and Levafix Brilliant Red E-4BA was noticeably higher
It can be assumed that most samples had a similar lifetime, with 2.8 and 3.0 compared to the undyed reference (2.1) and
which resulted in similar molecular properties. In an initial the remaining dyed samples (2.1–2.2). From the molar mass
assessment, we determined the limiting viscosities of 50 bed distributions, it can be inferred that both samples, Remazol
sheets to estimate their overall suitability for dry-jet wet spin- Black B gran 133% and Levafix Brilliant Red E-4BA, contained
ning in [DBNH] [OAc]. The predefined target range for the visc- a significantly higher amount of high molecular weight frac-
osities was 350–550 ml g−1. Samples below or beyond this tions (23.1% and 29.1%) than the rest of the post-consumer
range were not considered for further processing. The viscosity batches (14.3%–18.5%). Remazol and Levafix are reactive dyes,
distribution of the analyzed samples is illustrated in Fig. 3. which covalently bind to cellulose, whereas Indanthren dyes
Only 10% (5) of the bed sheets displayed viscosities below are precipitated on the cotton fiber. An effect on the molar
350 ml g−1, while 28% (14) showed values above 550 ml g−1. mass distribution caused through dyeing cannot be excluded,
The remaining 62% (31) of the samples were found adequate but seems unlikely in respect to the obvious heterogeneity of
to be used in the following experiments. post-consumer textile waste.

Dissolution of cotton and dry-jet wet spinning

The formation of cellulosic filaments from ionic liquid solu-
tions depends on the liquid thread’s ability to withstand capil-
lary and deformation forces.43 During the spinning process,
the cellulose solution is extruded through small nozzles,
where the cellulose molecules are pre-oriented. Further orien-
tation is induced by stretching of the resulting filaments in the
air-gap.44 The applied draw subsequently aligns the cellulose
molecules coaxially leading to increased breaking tenacities
and lower linear densities (i.e. titers), which are required for
textile applications. The stretchability of a polymer solution is
yet dependent on its rheological properties. Consequently, the
zero shear viscosities η0* and the dynamic moduli (G′, G″) at
their crossover point enable to predict the spinnability of the
Fig. 3 Viscosity distribution of the 50 hospital bed sheets analyzed; in cotton solutions (cf. Table 2, and for more details Table S2,
red, the number of samples chosen for dry-jet wet spinning. Fig. S3 as well as Fig. S4 in the ESI†).

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(Pa s) and dynamic moduli at their crossover point (G’ = G’’, Pa) dependent on the shear rate ω (1 s−1) and the spinning temperature T (°C), titers (dtex), breaking tenacities (cN/tex), and elongation

0.78 ± 0.12
0.78 ± 0.11
Table 2 Summary of the number of spinning trials per sample, fiber yields (%), cotton concentrations (wt%) of the spin dope, average rheological properties, such as zero shear viscosity η0*

0.72 ± 0.27
0.71 ± 0.06

0.70 ± 0.07
0.72 ± 0.09
0.71 ± 0.09
0.61 ± 0.16
0.75 ± 0.07

0.76 ± 0.22
Viscoelastic solutions usually show a Newtonian plateau at
lower shear rates until shear thinning occurs due to increased
shear stress.45 Supposing that the Cox Merz rule is valid, this

ftotal

n.a.
behavior allows the calculation of the zero shear viscosity η0*

Birefringence
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0.048 ± 0.007
0.048 ± 0.007
0.044 ± 0.017
0.044 ± 0.004

0.043 ± 0.004
0.045 ± 0.006
0.044 ± 0.005
0.038 ± 0.010
0.047 ± 0.004

0.047 ± 0.015
using the Carreau or the Cross model.36 η0* denotes the vis-
cosity of a polymer solution upon no shear stress applied. It is
directly affected by the concentration and temperature within

n.a.
Δn
the spinning process. In previous studies, we could show that

Tenacity/ Elongation/ Tenacity/ Elongation/

a η0* between 20 000–30 000 Pas indicates the optimum spin-

7.25 ± 1.03
12.5 ± 0.7
11.5 ± 1.3
12.4 ± 3.1

13.7 ± 1.1
14.3 ± 1.1
13.2 ± 1.5
14.2 ± 1.5
15.1 ± 2.1

13.8 ± 1.8
ning temperature if standard dissolving pulp is employed.35,46
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at break (%) of the fibers spun with draw ratio (DR) of 12 in conditioned and wet state, as well as the birefringence value Δn and total orientation ftotal of the fibers
However, these values deviate once waste materials such as

n.a.
%
paper or cotton are dissolved.16,38,47

33.7 ± 3.3
39.5 ± 3.2
45.0 ± 3.5
47.4 ± 4.1

53.4 ± 4.0
54.3 ± 2.3
51.2 ± 6.0
51.4 ± 2.6
57.0 ± 4.4

54.3 ± 4.3
As depicted in Table 2, the average zero shear viscosities of

(cN/tex)
the pre-consumer samples ranged between 16 400–31 100 Pas

Wet

n.a.
at 70 °C, while η0* for post-consumer cotton was significantly
higher with 32 700–78 200 Pas at optimum spinning tempera-

10.8 ± 0.6

12.8 ± 1.3

13.0 ± 1.4
14.3 ± 1.0
12.3 ± 1.9
13.1 ± 1.4
13.1 ± 1.6

13.1 ± 1.9
7.4 ± 1.4

8.9 ± 1.1
tures around 65 °C. This demonstrates that pre- and postcon-
sumer cotton waste show different ideal spinning tempera-

n.a.
%
Conditioned
tures and zero shear viscosities dependent on origin and pre-

40.3 ± 2.7
44.3 ± 1.4
45.5 ± 2.8
48.5 ± 4.1

56.4 ± 4.3
54.4 ± 8.4
54.7 ± 4.4
50.7 ± 8.8
59.8 ± 4.1

56.0 ± 4.7
treatment, and might thus demand different processing

(cN/tex)
conditions.

n.a.
Presumably, this deviation is due to a difference in the

1.4 ± 0.2
1.2 ± 0.1
1.0 ± 0.1
1.2 ± 0.1

1.4 ± 0.4
1.3 ± 0.2
1.4 ± 0.4
1.2 ± 0.2

1.2 ± 0.2
1.2 ± 02
molar mass distribution of the samples. The crossover point

Fiber yield/ Titer/

(COP) of storage and loss modulus (G′, G″) is influenced by the

dtex

n.a.
Fiber properties
amount of long and short polymer chains present in the spin
dope, as well as by the overall viscosity of the cellulose sample.
The narrower the molar mass distribution, the lower is the

20–74
0–17

0–25
T/°C η0*/Pa s ω/(1 s−1) G′ = G″/Pa DR wt%
substrate’s polydispersity index, and the higher is the COP

13

34
39
42
42
49

43
0
(G′ = G″). Moreover, lower limiting viscosities of the cellulose pulp

12
12
12
12

12
12
12
12
12
12
12
shift the COP to higher angular frequencies ω.48 In particular,
the enzyme pretreated pre-consumer cotton (Indanthren Blue
BC 3% A-EG and Indanthren Blue BC 3% EG-A) displayed
6996
2179
1630
3905

4554
4913
3484
4319
3131

4317
n.a.
noticeably lower average values for the G′ = G″ (1630–2179 Pa)
than the remaining pre- and postconsumer samples
(3131–6996 Pa). These results correspond to the molar mass
1.07
0.53
0.61
0.90

0.42
0.76
0.37
0.29
0.18

0.51
Spin dope rheology

n.a.
distributions depicted in Table 1 and in Fig. 2a & b. Inevitably,
these properties affected the spinnability of the respective

812 200
31 100
31 100
16 400
26 500

47 500
37 200
41 200
78 200
55 900

32 700
cotton solutions, which is reflected in the fiber yields summar-
ized in Table 2.
The highest yields could be obtained with pre-consumer
70
70
70
70

65
65
65
65
65
65
65
Indanthren Blue BC 3% EG-A (20–74%). Neither electron beam
Cotton/

13–14
13–14

radiation nor A led to quantitative fiber amounts (0–25%). It is

Trials wt%

13
13

13
13
13
13
13
13
13

unclear whether this discrepancy can solely be attributed to

the narrow molar mass distribution,41 or to a lack of optimiz-
12
3

1
2

1
1
1
1
1
1
1

ation. Despite similar COPs, all spinnable post-consumer

samples resulted in yields between 34–49% at 5 °C lower spin-
Indanthren Brilliant Green FBB Coll

ning temperatures. An exception was Levafix Brilliant Red

Indanthren Blue BC 3% e-beam

Remazol Brilliant Blue R spec

E-4BA, which was not spinnable at all because of its obvious

Indanthren Blue BC 3% EG-A
Indanthren Blue BC 3% A-EG

Indanthren Brilliant Red FBB

Remazol Black B gran 133%

Levafix Brilliant Red E-4BA

gel character implied by the absence of the COP. In this

Indanthren Blue BC 3% A

Levafix Blue E-GRN gran

context it also needs to be noted that fiber yields can only be

regarded as tentative indicators for a substrate’s spinnability
Post-consumer
Pre-consumer

as the whole study was conducted on a lab-scale equipment,

where material losses cannot be avoided because of batch pro-
cessing. Despite the high yields reached with the EG-A
Undyed
Sample

batches, it is evident that the post-consumer samples showed

higher yields on average. The spinning quality would thus

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the Moduli of Toughness obtained for all regenerated post-

consumer fibers displaying values of 60.0–69.5 MPa, whereas
the pre-consumer samples only yielded moduli up to 53.6 MPa
(cf. Table S3 in the ESI†).
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These results agree with earlier studies describing the re-

cycling of cotton waste in NMMO or [DBNH] [OAc].16,17,20 The
choice of the dye did not appear to have an impact on the fiber
properties apart from Levafix Brilliant Red E-4BA, which was
not spinnable due to gel formation.
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Yarn spinning
All batches of the spun Indanthren Blue BC 3% dyed pre-con-
sumer cotton were combined for the yarn spinning process. All
other samples were processed to yarns separately. The fibers
were spin finished to control their antistatic and cohesion pro-
Fig. 4 Average breaking tenacities (cN/tex) of the spun fibers in con- perties in the yarn spinning process. The strength of the spun
ditioned state as a function of the average Young’s Modulus (GPa).
yarns depends on the fiber strength and the frictional resis-
Viscose, Lyocell, and Standard Ioncell Fibers were added as a reference.
tance to slippage.49 The angle of fiber inclination increases
with increasing yarn twist. At the same time, the component of
fiber strength in the yarn axis decreases. Otherwise, the fric-
better be described by the maximum draw ratio extruded fila- tional resistance between the fiber raises as the yarn twist is
ments can withstand; its assessment was however without the increased until the fiber slippage in the yarn is eliminated. In
scope of this study. the short-staple yarn spinning, 30–70% of the fiber strength
The resulting fiber properties (see Table 2 and Fig. 4) show can be exploited in the yarn.50 The properties of the spun
a considerable difference between the spun pre- and post-con- yarns are summarized in Table 3. Similar to the fiber pro-
sumer samples. As mentioned in the experimentals, all fibers perties, the yarn spun from Indranthren Blue BC 3% yielded
were stretched with a draw ratio of 12, which means that the the lowest tenacity 25.0 cN/tex with an elongation at break of
take-up velocity of the godets collecting the fibers is 12 times 7.6%, while the dyed post-consumer samples showed tenaci-
higher than the extrusion velocity of the spin dope. At similar ties of 28.8–32.7 cN/tex and elongations of 6.7–7.1%.
concentrations (13–14 wt%), this leads to fibers with compar-
able linear densities (1.0–1.4 dtex). The variation within this Fabrics and demonstration products
parameter usually results from differences in the solubility of All fabrics used for the wash fastness and rubbing tests as well
the cotton pulp during the dissolution stage, which finally as the demonstration products (see Fig. 5) were knitted from the
influences the real concentration of the cotton solution. It was yarns listed above as discussed in earlier publications.35,51 The
observed that untreated cotton pulp dissolved better than pre- baby jacket was manufactured using the samples obtained from
treated one, which formed undissolved aggregates in the spin Indanthren Blue BC 3%, whereas the scarf was knitted from
dope presumably due to hornification after wet processing and Remazol Brilliant Blue R spec dyed samples. The fabrics below
drying. represent the remaining samples produced from the recycled
The breaking tenacities and elongations of the spun post- fibers on the right and the dyed waste fabrics on the left.
consumer cotton (50.4–59.0 cN/tex, 12.3–14.3%) in con-
ditioned state were significantly higher than the values of the Dyes in the spinning process
pre-consumer samples (40.3–48.5 cN/tex, 7.4–12.8%). This Whether the original color of a waste fabric can be reused in
trend also continued in wet state (51.2–54.3 cN/tex, 13.2–14.2% new textile fibers depends on a variety of factors. Concerning
for post-consumer; 39.5–47.4 cN/tex, 11.5–12.5% for pre-consu-
mer), and is reflected in the Young’s Modulus of the fibers
(see Fig. 4 and Table S3,† as well as average stress strain curves
Table 3 Mechanical properties of spun yarns (single thread)
in Fig. S5 & S6†). A similar trend for the total orientation of
the fibers could not be observed (cf. Table 2). Titer/ Tenacity/ Elongation/
Although all fibers exceeded the properties of commercial Sample tex (cN/tex) %
Lyocell and Viscose, the recycled post-consumer fibers Pre-consumer
appeared on average stronger and more flexible than the ones Indanthren Blue BC 3% 17.8 ± 1.5 25.0 ± 4.7 7.6 ± 0.9
produced from pre-consumer waste, exhibiting Young’s Post-consumer
Moduli from 12.0–14.4 GPa and 13.1–17.0 GPa, respectively. Indanthren Brilliant Red FBB 21.7 ± 1.7 28.8 ± 3.8 6.9 ± 0.5
Moreover, the post-consumer samples yielded also 6–25% Indanthren Brilliant Green FFB Coll 20.8 ± 1.8 28.9 ± 3.6 6.4 ± 0.5
Remazol Black B gran 133% 25.3 ± 0.5 29.0 ± 3.4 7.1 ± 0.5
better tenacities compared to the Ioncell fibers spun from Remazol Brilliant Blue R spec 21.2 ± 1.0 32.7 ± 3.9 6.9 ± 0.5
bleached pre-hydrolysis kraft pulp. This also corresponds to Levafix Blue E-GRN gran 21.5 ± 0.9 31.4 ± 4.4 6.7 ± 0.6

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attach to the ionized cellulose via etherification of the vinyl

sulphone groups.53 Competing hydrolysis reactions can
however cause a restrained substantivity.54 On the contrary,
Levafix dyes form covalent bonds with cellulose through a
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nucleophilic substitution reaction of their halo quinoxaline

units. They contain two reactive groups and may form two
dye-fiber bonds. Their reactivity is lower compared to
dichloro-s-triazine dyes and they might undergo hydrolysis
reactions in acidic environment.55 Finally, the stability of a
dye within a recycling process strongly depends on its chemi-
Open Access Article. Published on 18 September 2019. Downloaded on 2/12/2025 5:14:56 AM.

cal structure, the nature of its interaction with cellulose and

the solvent.
In initial dissolution experiments (cf. Table S1 in the ESI†),
we found all dyes apart from Indanthren Blue BC 3% and
Indanthren Brilliant Red FBB, soluble in [DBNH] [OAc]. The
Fig. 5 Left: Baby jacket produced from the Indanthren Blue BC 3% yarn same applied for almost all dyed cotton fabrics, excluding the
knitted in 2 × 1 rib on top and in interlock structure below. Right: Scarf sample dyed with Levafix Brilliant Red E-4BA, where aggrega-
knitted from Remazol Brilliant Blue R spec yarn. Below: Dyed waste
tions of undissolved fibers could be observed under the micro-
fabrics on the left and fabrics made from the remaining recycled fibers
on the right. scope. The insolubility of the two Indanthren dyes, however,
did not affect the quality of the resulting spin dopes. The dyes
and cellulose formed a homogenous solution in the ionic
post-consumer waste, the dye needs to exhibit a good color liquid, which led to regenerated fibers that displayed a
fastness towards washing and rubbing so that the waste uniform distribution of dye throughout the fiber cross-
garment still shows a sufficient color intensity at the end of section.27,30 Only Remazol dyes leached into the spin bath
its lifecycle. When recycled in a dry-jet wet spinning process, causing color fading, most likely due to insufficient fixation
dyes additionally require to tolerate the chemical environ- during the dyeing step.31 Table 4 summarizes the CIELab para-
ment thereof, including elevated temperatures and pH, and meters lightness L*, a* (red-green axis), and b*(yellow-blue
should not change the rheological properties of the spin axis) as well as the overall color difference ΔE in the CIELab
dope.25,52 Indanthren Blue BC 3%, Indanthren Red FBB coll, space. ΔE is a tool to assess the similarity of colors during
and Indanthren Brilliant Green FBB coll represent vat dyes, quality control. Values of 0–0.5 describe no change, 0.5–1.0 an
which have already been studied as colorants for spin dyeing almost imperceptible change (usually not visible by the
in the Lyocell process yielding excellent color fastness.28–30 human eye), 1.0–2.0 a small color difference, 2.0–4.0 a percei-
Their oxidized form is usually insoluble in water, which vable difference, and 4.0–5.0 a rarely tolerated change, whereas
makes it possible to precipitate them on the fiber surface values above 5.0 denote a different color.
through a sequence of reduction and oxidation reactions. Vat All dyes showed a noticeable color difference (ΔE =
dyes also show a high thermal stability due their aromatic 8.8–25.6), with Indanthren dyes (ΔE = 8.8–14.) and Levafix
structure formed by antraquinone units. Likewise, reactive (ΔE = 9.2) resulting in similar fastness properties. During the
dyes with antraquinone (Remazol Brilliant Blue R spec or dissolution of cotton, [DBNH] [OAc] creates an alkaline
Levafix Blue E-GRN gran) have been reported to be particu- environment that enables the conversion of vat dyes into their
larly durable towards laundering, elevated temperatures, and reduced form. This can induce breakages of the hydrogen
bleaching32,33 especially compared to azo chromophores bonds between cellulose and the respective dyes, which can
(Levafix Brilliant Red and Remazol Black B gran 133%). affect the final shade of the regenerated fibers. On the con-
Remazol dyes exist as mono (Remazol Brilliant Blue R spec) trary, an alkaline cleavage of the ether bond between cellulose
and bifunctional colorants (Remazol Black B gran 133%) and and the Levafix dyes seems rather unlikely.

Table 4 Color difference in the CIELab space (ΔE) of the dyed fabrics and the fibers after spinning

Waste fabric Recycled regenerated fibers

Samples L* a* b* L* a* b* ΔE

Indanthren Blue BC 3% 69.0 ± 0.3 −4.9 ± 0.3 −22.2 ± 1.1 56.6 ± 1.1 −6.6 ± 0.1 −14.0 ± 0.3 14.9
Indanthren Brilliant Red FBB 40.5 ± 1 49.1 ± 0.6 6.9 ± 0.4 39.5 ± 0.8 38.1 ± 0.7 12.9 ± 0.3 12.6
Indanthren Brilliant Green FBB Coll 37.0 ± 0.5 −46.9 ± 0.4 −1.4 ± 0.1 34.5 ± 0.4 −38.4 ± 0.1 −0.9 ± 0.1 8.8
Remazol Black B gran 133% 18.7 ± 0.3 −5.0 ± 0.1 −16.2 ± 0.2 35.6 ± 1.2 15.6 ± 0.3 6.2 ± 0.2 25.6
Remazol Brilliant Blue R spec 43.0 ± 0.6 −1.8 ± 0.1 −39.7 ± 0.3 56.9 ± 3.1 0.7 ± 0.7 −20.7 ± 0.4 23.6
Levafix Brilliant Red E-4BA 41.9 ± 0.3 62.0 ± 0.3 0.01 ± 0.2 n.a. n.a. n.a. n.a.
Levafix Blue E-GRN gran 37.5 ± 0.9 −1.5 ± 0.1 −31.97 ± 0.3 35.3 ± 1.4 −3.5 ± 0.5 −23.3 ± 0.6 9.2

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crystalline structure transforms from cellulose I to cellulose II.

Besides, the dissolution and regeneration is also accompanied
by a change of the surface morphology of the regenerated
fibers.16 The result is an increased luster, which for example
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becomes evident in the color of the fibers.

Eventually, it can be assumed that the observed color
changes are a combination of surface phenomena, insufficient
boil-off after dyeing, as well as chemical reactions occurring in
the alkaline environment of [DBNH] [OAc]. Apart from
Remazol Black B 133% and Levafix Brilliant Red E-4BA, all
Open Access Article. Published on 18 September 2019. Downloaded on 2/12/2025 5:14:56 AM.

dyed waste fabrics nonetheless translated to brightly colored

fibers that certainly can be employed in textile industry (cf.
Fig. 6 UV spectra of the spinbath after spinning with Remazol Blue R
Fig. 5).
spec and Remazol Black B 133%, as well as of the pure dyes in water.

Color fastness to washing and rubbing

The color leaching of Remazol Brilliant Blue R spec and The color fastness to washing and color fastness to rubbing
Black B gran 133% was followed by the largest alterations are the most typical color fastness tests for textiles. They
(ΔE = 23.6; 25.6). As displayed in Fig. 6, the absorbance predict how much color fades and stains white garments
maximum of Remazol Brilliant Blue R spec did not experience during the laundering or rubbing. Vat dyes (Indanthren) have
any significant shift (590 nm to 587 nm) throughout the spin- good all-round fastness properties because of their water inso-
ning process, while the absorbance band of Remazol Black B lubility. Reactive dyes (Levafix and Remazol) show in particular
133% shifted from 597 nm to 574 nm. According to the Color good wet fastness due to covalent bonding between the dye
Index, Remazol Black B 133% (C.I. Reactive Black 5) exhibits a molecule and cellulose. Table 5 summarizes the wash fastness
rather poor alkali resistance, but it remains unclear whether results of all dyed waste fabrics and the fabrics manufactured
the strong color change can be attributed to a degradation of from the dry-jet wet spun fibers.
the chromophore in [DBNH] [OAc], or to an insufficient As described before, Remazol Brilliant Blue R spec is a
fixation of dye during the dyeing step. monofunctional vinyl sulphone dye. Although it forms a
Moreover, the spinning process triggered an increase of b* covalent bond with cellulose, it also undergoes a competing
(yellow-blue axis) in all samples, and raised the lightness L* of hydrolysis reaction with water during the dyeing process. The
the Remazol dyed samples, while the remaining samples (i.e. same applies for Remazol Black B gran, but it shows a higher
Levaifx, Indanthren) showed a slight decrease of L*. For a* fixation rate because of two reactive groups. Similarly, the
(red-green axis), no particular trend could be observed. dichloroquinoxaline dyes Levafix Brilliant Red E-4BA and
Without a doubt, any recycling process that consists of Levafix Blue E-GRN gran can partially hydrolyze during dyeing
reshaping polymeric material also brings about color changes. and this may reduce their wash fastness.55 However, sufficient
When cotton is dissolved and subsequently coagulated, its rinsing and boiling-off after dyeing removes the hydrolyzed

Table 5 Wash fastness of cotton and regenerated cellulosic fabrics according to the greyscale

Numerical rating for staining

Change in Cellulose
Sample colour Wool Acrylic Polyester Polyamide Cotton acetate

Cotton
Indanthren Blue BC 3% 5 5 5 5 5 5 5
Indanthren Brilliant Red FBB 4–5 5 5 5 5 5 5
Indanthren Brilliant Green FBB Coll 5 4–5 5 5 5 5 5
Remazol Black B gran 133% 4–5 5 5 5 5 5 5
Remazol Brilliant Blue R spec 5 5 5 5 5 5 5
Levafix Brilliant Red E-4BA 5 5 5 5 5 4–5/5 5
Levafix Blue E-GRN gran 5 5 5 5 5 5 5
Ioncell (from recycled cotton waste)
Indanthren Blue BC 3% 5 5 5 5 5 5 5
Indanthren Brilliant Red FBB 5 5 5 5 5 5 5
Indanthren Brilliant Green FBB Coll 5 5 5 5 5 5 5
Remazol Black B gran 133% 4–5/5R 5 5 5 5 5 5
Remazol Brilliant Blue R spec 5 5 5 5 5 5 5
Levafix Brilliant Red E-4BA n.a. n.a. n.a. n.a. n.a. n.a. n.a.
Levafix Blue E-GRN gran 5 5 5 5 5 5 5

5608 | Green Chem., 2019, 21, 5598–5610 This journal is © The Royal Society of Chemistry 2019
 View Article Online

Green Chemistry Paper

Table 6 Rubbing fastness of cotton and regenerated cellulosic fabrics perties of the regenerated fibers were shown to be dependent
on the origin of the waste substrate and the pretreatments
Numerical rating of employed. This is reflected in the tenacities and elongations at
staining
break of 40.3–48.5 cN/tex 7.4–12.8% for pretreated pre-consu-
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

Sample Dry Wet mer waste, and 50.7–59.8 cN/tex and 12.3–14.3% for untreated
Cotton post-consumer cotton. Beside of Levafix Red E-4BA, the dyes
Indanthren Blue BC 3% 4–5 2 did not affect the solubility of the cotton substrates in [DBNH]
Indanthren Brilliant Red FBB 4–5 2 [OAc]. All translated colors changed throughout the spinning
Indanthren Brilliant Green FBB Coll 3–4 2
Remazol Black B gran 133% 2–3 1–2 process (ΔE = 8.8–25.6) most likely due to alterations in the
macromolecular structure of cellulose and leaching of the dyes
Open Access Article. Published on 18 September 2019. Downloaded on 2/12/2025 5:14:56 AM.

Remazol Brilliant Blue R spec 4–5 3

Levafix Brilliant Red E-4BA 4 2 into the spin bath (i.e.in particular Remazol Black B 133%).
Levafix Blue E-GRN gran 5 3
Nevertheless, most samples still displayed bright colors, which
Ioncell (from recycled cotton waste) were suitable for the manufacturing of fabrics and demonstra-
Indanthren Blue BC 3% 5 5
Indanthren Brilliant Red FBB 4–5 4 tor products. The wash and rubbing fastness increased after
Indanthren Brilliant Green FBB Coll 4 3–4 spinning as the colorants were incorporated homogenously
Remazol Black B gran 133% 5 4–5 into the fiber matrix. Eventually, the recyclability of dyed
Remazol Brilliant Blue R spec 5 4–5
Levafix Brilliant Red E-4BA n.a. n.a. cotton will demand adequate labelling of the chemicals
Levafix Blue E-GRN gran 5 4–5 involved to enable proper reprocessing at the end of its life-
cycle. It can be concluded that vat dyes and reactive dyes with
anthraquinone units have the greatest potential to be re-used
dyes completely. This study demonstrated an excellent wash in dry-jet wet spinning. In terms of sustainability, colored
fastness for both cotton and regenerated cellulosic fabrics, post-consumer waste cotton requires less processing than pre-
regardless of the dyes employed (cf. Table 5). consumer fabrics as its molar mass distribution tends to be
Table 6 describes the rubbing fastness of the fabrics before adjusted to fit the spinning parameters by wearing and laun-
and after recycling. The low rubbing fastness of the dyed waste dering. Eventually, the manufacture of a scarf successfully
fabrics arises from the superficial presence of the dye. It may demonstrated that worn jeans (i.e. denim fabrics) can be
cause the formation of heavy shades, inadequate washing at recycled into new, high-quality fibers that retain most of their
the end of dyeing, and the coloration of only a few molecules color using the Ioncell™ process.
at the textile-air interface. Besides, it might affect the water
solubility of the dyes and lead to a weak dye-fibre attachment
on the surface layer. Overall, wet rubbing fastness tends to Conflicts of interest
produce lower results compared to dry rubbing, which is due
to the partly solubilization of the dye and its migration to the There are no conflicts to declare.
surface of colored fabric. Consequently, the regenerated cell-
ulose fibers showed a significantly better rubbing fastness as
the dyes were homogenously distributed in the fiber structure Acknowledgements
by the spinning process.
This project has received funding from the European Union’s
Recovery of the ionic liquid [DBNH] [OAc] Horizon 2020 research and innovation programme under
An entirely green recycling process demands the processing grant agreement No. 646226. The authors also gratefully
chemicals to be recyclable in the same manner as the waste acknowledge Leena Katajainen (Aalto University) and VTT
substrate, which it upcycles. After spinning, the ionic liquid (Finland) for their support in material pretreatment, as well as
[DBNH] [OAc] accumulates in the aqueous coagulation bath. Kaniz Moriam, Mikaela Trogen, Karl Mihhels, Yibo Ma, Sherif
Therefore, the water must be removed from the ionic liquid to Elsayed and Hilda Zahra (Aalto University) for assisting in
a tolerable residual content, while at the same time accumu- fiber spinning and dope preparation.
lated decomposition products of the solute must be elimi-
nated. These approaches are part of our on-going research and
will be published in more detail soon. References
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5610 | Green Chem., 2019, 21, 5598–5610 This journal is © The Royal Society of Chemistry 2019